KR20110014606A - Polymer pen lithography - Google Patents

Abstract

The present disclosure relates to a method of printing indicia on a substrate using a tip array of elastomeric compressible polymers. The tip array can be manufactured using traditional photolithography methods and can be customized to have any desired number and / or arrangement of tips. Numerous (eg, 15,000 or more than 11 million) copies of the pattern can be made in a parallel fashion in as little as 40 minutes.

Description

Polymer pen lithography {POLYMER PEN LITHOGRAPHY}

Cross Reference to Related Applications

The present invention discloses US Provisional Serial No. 61 / 047,910, filed April 25, 2008, US Provisional Serial No. 61 / 049,679, filed May 1, 2008, and filed on June 27, 2008. Claims under 35 USC §119 (e) of US provisional application Ser. No. 61 / 076,199, the disclosures of which are hereby incorporated by reference in their entirety.

Statement of Government Interests

The invention has been completed with the support of the US Government in accordance with the National Science Foundation (NSF-NSEC) Grant No. EEC-0647560 and the National Cancer Institute (NCI-CCNE) Grant No. 5 U54 CA 119341. The United States government has certain rights in this invention.

Lithography includes integrated circuits, information storage devices, video screens, micro-electromechanical systems (MEMS), miniaturized sensors, microfluidic devices, biochips, photonic band gap structures and diffractive optics. It is used in various fields of modern science and technology (1-6) . In general, lithography can be divided into two classes, parallel replication and serial writing, based on patterning strategies. Parallel replication methods such as photolithography (7) , contact printing (8-11) , and nanoimprint lithography (12) are useful for high throughput, large area patterning. However, most of these methods can only duplicate patterns predefined by the continuous writing method, and thus cannot be used to randomly generate different patterns (ie, one mask provides a set of structures). . In contrast, continuous writing methods, including electron beam lithography (EBL), ion beam lithography, and multiple scanning probe microscopy (SPM) based methods (13-16) , have high resolution and registration. Pattern can be generated, but throughput is limited ( 17, 18 ). In fact, researchers have only recently patterned molecular-based materials on a square centimeter area using two-dimensional cantilever arrays for dip-pen nanolithography (DPN). I found out how to produce the structure (19, 20 ).

C. A. Mirkin, ACS Nano 1, 79 (2007). K. Salaita, et al., Nat. Nanotech. 2, 145 (2007). D. S. Ginger, et al., Angew. Chem. Int. Ed. 43, 30 (2004). Y. Xia, G. M. Whitesides, Angew. Chem. Int. Ed. 37, 551 (1998). Y. Xia, G. M. Whitesides, Ann. Rev. Mater. Sci. 28, 153 (1998). M. Qi et al., Nature 429, 538 (2004). T. Ito, S. Okazaki, Nature 406, 1027 (2000). Y. L. Loo, et al., J. Am. Chem. Soc. 124, 7654 (2002). Z. Zheng, et al., J. Am. Chem. Soc. 128, 7730 (2006). A. Kumar, G. M. Whitesides, Appl. Phys. Lett. 63, 2002 (1993). M. N. Yousaf, et al., Proc. Natl. Acad. Sci. 98, 5992 (2001). S. Y. Chou, et al., Science 272, 85 (1996). S. Xu, et al., Langmuir 15, 7244 (1999). M. Geissler, Y. Xia, Adv. Mater. 16, 1249 (2004). B. D. Gates et al., Chem. Rev. 105, 1171 (2005). R. D. Piner, et al., Science 283, 661 (1999). S. Kramer, et al., Chem. Rev. 103, 4367 (2003). R. Maoz, et al., Adv. Mater. 11, 55 (1999). S. Lenhert, et al., Small 3, 71 (2007). K. Salaita et al., Angew. Chem. Int. Ed. 45, 7220 (2006). S. Hong, C. A. Mirkin, Science 288, 1808 (2000). L. M. Demers et al., Science 296, 1836 (2002). K.-B. Lee, et al., Science 295, 1702 (2002). For example, fabrication of a 10 μm × 10 μm MHA shape DPN on a gold substrate using a traditional Si 3 N 4 cantilever (curvature radius = 20-60 nm) takes approximately 30 minutes. E. Delamarche et al., Langmuir 19, 8749 (2003). T. W. Odom, et al., Langmuir 18, 5314 (2002). H. Zhang, et al., Nano Lett. 4, 1649 (2004). X. Wang et al., Langmuir 19, 8951 (2003).

DPN uses an "ink" coated atomic force microscopy (AFM) cantilever to deliver soft or hard materials to surfaces in a "constructive" manner with high registration and sub-50 nm resolution ( 3, 16, 21-23 ). When combined with high density cantilever arrays, DPN is a versatile and powerful tool for constructing molecular-based patterns over a relatively large area with moderate throughput (1) . The limitations of DPN include: 1) the inability to work quickly and easily across micro and nano length scales in a single experiment (usually a sharp tip is optimized to produce nanoscale features, or blunt tips Used to create micro scale shapes) 24 ; And 2) the need for fragile and expensive two-dimensional cantilever arrays to achieve large area patterning. Indeed, there is no simple strategy for rapidly patterning molecular-based shapes with sizes ranging from nanometers to millimeters in a parallel, high throughput and direct manner. Accordingly, there is a need for a lithography method that can provide high resolution, registration and throughput, and soft material compatibility and low cost patterning capability.

summary

The present disclosure relates to a method of printing indicia on a substrate surface using a polymer tip array. More specifically, a method of printing indicia on a substrate surface using a tip array comprising a compressible polymer, each comprising a plurality of non-cantilevered tips, each having a radius of curvature of less than about 1 μm. Is initiated.

Thus, in one aspect, (1) coating a tip array with a patterning composition comprising a compressive elastomeric polymer having a plurality of tips each having a radius of curvature of less than about 1 μm, and (2) during the first contact period And contacting all or substantially all of the coated tips of the array at a first contact pressure with the substrate surface, thereby depositing a patterned composition on the substrate surface to produce a substantially uniform feature size of less than 1 μm. And preferably also a method of printing indicia on a substrate surface comprising forming indicia having a substantially uniform feature shape. The coating includes adsorbing or absorbing the patterned composition onto the tip array. The method may further comprise moving only one of the tip array or the substrate surface, or moving both the tip array and the substrate surface, and repeating the contacting step during the second contact period and under the second contact pressure. Can be. The first and second contact periods and pressures may be the same or different. The contact pressure can be controlled by controlling the z-piezo of the piezo scanner on which the substrate or tip array is mounted. Lateral motion between the tip array and the substrate surface to form indicia comprising dots, lines (e.g., straight lines or curves formed from individual points or continuously), preselected patterns, or any combination thereof. For example, by changing the movement and / or limiting the movement. Controlling the contact pressure and / or contact duration can produce indicia, for example dots with controllable and reproducible size. The indicia formed by the disclosed method has a minimum of less than 1 micron, for example 900 nm or less, 800 nm or less, 700 nm or less, 600 nm or less, 500 nm or less, 400 nm or less, 300 nm or less, 200 nm or less, 100 nm or less, 100 nm or less, or 80 nm or less. It may have a shape size of (eg, dot size or line width).

Another aspect of the disclosure provides a method of leveling a tip array disclosed herein with respect to a substrate surface.

One method comprises backlighting the tip array with incident light to cause an internal reflection of the incident light from the inner surface of the tip, the tip of the tip array and the substrate surface together between the substrate surface and a subset of the tip along the z axis. Bringing up to the point of contact, where an increase in the intensity of light reflected from a subset of the tip in contact with the substrate surface is indicative of a contact, while a change in the intensity of light reflected from the other tip is a non-contacting tip And tilting one or both of the tip array and the substrate surface relative to each other in response to a difference in intensity of reflected light from the inner surface of the tip to achieve contact between the non-contact tip and the substrate surface. Steps. The tilting step may be performed one or more times along any one of the x, y and z axes to smooth the array of tips with respect to the substrate surface. The reflected light can be observed by propagating at least some of the reflected light back through the tip array material in the direction of incident light if the tip array material is at least translucent. Preferably all substrates on which the tip array is mounted are also at least translucent or transparent.

Another method is to back-illuminate the tip array with the incident light to cause an internal reflection of the incident light from the inner surface of the tip, and the tip and substrate surface of the tip array along the z axis to cause contact between the tip of the tip array and the substrate surface. Bringing together, further compressing a subset of the tips so that the intensity of the reflected light from the tips increases as a function of the degree of compression of the tips relative to the substrate surface and further along one or both of the tip arrays and substrates along the z axis towards each other. Moving, tilting one or both of the tip array and the substrate surface relative to each other in response to a difference in intensity of reflected light from the inner surface of the tip to achieve a substantially uniform contact between the substrate surface and the tip. Include. The tilting step is performed one or more times along any one of the x-axis, y-axis, and z-axis to smooth the array of tips with respect to the substrate surface, as determined, for example, by the uniform intensity of the reflected light from the tip. Can be. The reflected light can be observed by propagating at least some of the reflected light back through the tip array material in the direction of incident light if the tip array material is at least translucent. Preferably all substrates on which the tip array is mounted are also at least translucent or transparent.

Another aspect of the disclosure is to provide a tip array. The tip array may include a plurality of tips arranged in a regular periodic pattern. The radius of curvature of the tip may be less than about 0.5 μm, less than about 0.2 μm, or less than about 100 nm. The tips may have the same shape or may be pyramid shaped. The polymer of the tip array may have a compression modulus of about 10 MPa to about 300 MPa. The polymer may be hookean under pressure of about 10 MPa to about 300 MPa. The polymer may be crosslinked. The polymer may comprise polydimethylsiloxane (PDMS). PDMS can be trimethylsiloxy terminated vinylmethylsiloxane-dimethylsiloxane copolymer, methylhydrosiloxane-dimethylsiloxane copolymer or mixtures thereof. The tip array can be secured to a common substrate. The common substrate may comprise a rigid support such as glass. Alternatively, the common substrate can be fixed to the rigid support. The common substrate may comprise an elastomeric layer that may comprise the same polymer as the tip array or may be an elastomeric polymer different from the tip array. The tip array, common substrate and / or rigid support may be at least translucent and transparent. In certain embodiments, the tip array, common substrate, and rigid support, when present, are at least translucent or transparent, respectively. The tip array and common substrate (eg, elastomer layer) may have a height of less than about 200 μm, preferably less than about 150 μm, or more preferably about 100 μm.

Another aspect of the invention provides a method of making a tip array as disclosed herein. The method includes forming a master comprising an array of recesses in the substrate spaced by lands; Filling said recess with a prepolymer mixture comprising a prepolymer and optionally a crosslinking agent and covering said lands; Curing the prepolymer mixture to form a polymer structure; And separating the polymer structure from the master. The method may further comprise forming a well in the substrate and wet etching the substrate anisotropically to form the recess into a pyramidal recess. The method may further comprise covering the filled and coated substrate with a planar glass layer prior to curing.

A is a schematic diagram of a polymer pen lithography configuration in Figure 1, B is a photograph of the 11 million pen array, C is the SEM image of the polymer pen array. The average tip radius of curvature is 70 ± 10 nm (inset).
Figure 2 A is an optical image of the x 360㎛ section 480㎛ of (6x6 in each block), gold dot array on the 1 million (28,000 pyramid-shaped tip with the pen array having a) a silicon (silicon) substrate. B is the MHA dot size as a function of relative z-piezo extension. The results were obtained using a polymer pen array with 15,000 pyramidal tips at 25 ° C. with 40% relative humidity. C is an optical image of a gold square array created with different z piezoelectric extensions (using a pen array with 28,000 pyramidal tips). D is an optical microscope image of a multi-dimensional gold circuit produced by polymer pen lithography. The inset shows an enlarged image of the center of the circuit.
Of Fig. 3 A is an SEM image of a typical area of the miniature replica of the Beijing Olympic logo about 15,000 in 2008. B is an enlarged optical image of a representative replica. Inset shows an enlarged SEM image of the letter "e".
In FIG. 4, A is an SEM image of a polymer pen array with a glass support, and B is an SEM image of a polymer pen array without a glass support. Polymer pen arrays with a glass support are homogeneous over the entire area, while those without a glass support appear wavy.
Figure 5 A is a photograph of the etched pattern on the gold four inches Si wafer manufactured by the Polymer Pen Lithography using the 11 million pen array shown in Figure 1 B. The areas patterned by the pen array are highlighted by white dotted lines. At the center of the pen array, more than 99% of the pens uniformly deliver the MHA ink to the substrate during the polymer pen lithography process to form a contoured structure. Reduced activity appears at the periphery of the array due to poor contact between the pen and the Si substrate in the periphery region of the array. This is from current mechanical sample holder limits. B is an optical microscope image of the gold pattern in A prepared by polymer pen lithography. Inset is an enlarged image. The image shows that all the structures intended for this experiment were formed.
6 shows MHA dot size as a function of tip-based contact time. Dot size increases with increasing tip-based contact time at constant contact (pressure) (initial contact). The results were obtained using a polymer pen array with 15,000 pyramidal tips at a relative humidity of 50% (circle) and 90% (square) and a temperature of 23 ° C.
7 is a fluorescence microscope image of anti mouse IgG array prepared by polymer pen lithography.
8 is a schematic diagram of an array of tip arrays, piezoelectric scanners, and substrate surfaces with respect to a light source, used to smooth the tip array with respect to the substrate surface.

details

Polymer pen lithography is a direct-write method of delivering molecular aggregates in a positive printing form. In contrast to DPN and other SPM based lithography, which typically uses hard silicon-based cantilever, polymer pen lithography uses elastomeric tips 25, 26 without cantilever as ink delivery tools. The tip preferably consists of polydimethylsiloxane, PDMS. The preferred polymer pen array (FIG. 1) comprises thousands of tips, preferably in the form of pyramids, which can be prepared using a master made by traditional photolithography and subsequent wet chemical etching (FIG. 1A). . The tip is preferably adhered to a rigid support (e.g. glass, silicon, quartz, ceramic, polymer or any combination thereof), for example prior to or through the curing process of the polymer. It is preferably connected by a common substrate comprising a thin polymer backing layer (thickness 50-100 μm). The rigid support preferably has a very stiff, highly planar, surface on which the array is mounted (eg, silica glass, quartz, etc.). The rigid support and thin backing layer significantly improve the uniformity of the polymer pen array over a large area, such as a 3 inch wafer surface (FIGS. 1B, 4) and allow for smooth, uniform and controlled use of the array. The ink is delivered to the contact point when the sharp tip of the polymer pen contacts the substrate. (FIG. 1A)

The amount of light reflected from the inner surface of the tip increases significantly when the tip contacts the substrate. Thus, translucent or transparent elastomeric polymer pen arrays enable visual confirmation of the point at which all the tips are in contact with the underlying substrate, making it possible to handle the smoothing of the array, which is otherwise a very difficult task, in an experimentally simple manner. Thus, preferably, at least one of the array tip, backing layer and rigid support is at least translucent and preferably transparent.

Polymer pen lithography experiments were performed with a Nscriptor ^™ system (NanoInk Inc., Ill.) Equipped with a 90 μm closed loop scanner and commercial lithography software (DPNWrite ^™ , DPN System-2, NanoInk Inc., Illinois). Depending on the intended use, the pitch of the pen array is intentionally determined between 20 μm and 1 mm, corresponding to pen densities 250,000 / cm 2 and 100 / cm 2, respectively. Larger pitch arrays are needed to make large shapes (micron or millimeter scale), but can also be used to make nanoscale shapes. All pens are very uniform in size and shape with an average tip radius of 70 ± 10 nm (FIG. 1C). In theory, this value can be significantly reduced by using higher quality masters and harder elastomers. For the examples below, the tip arrays used included 15,000 or 28,000 pyramid pens, but arrays with as many as about 11,000,000 pens have also been used for patterning structures (FIG. 5).

In a general experiment, a pen array (size 1 cm 2) is immersed in a saturated solution of 16-merctohexadecanoic acid (MHA) in ethanol for 5 minutes and rinsed with ethanol to apply ink. The inked pen array was brought into contact with the gold surface for 0.1 seconds, producing a 1 μm diameter MHA dot pattern on a thermally evaporated polycrystalline gold substrate (25 nm Au with a 5 nm Ti adhesive layer coated on Si). It was used to The process of contacting the gold substrate was repeated 35 times to produce a 6 × 6 array of MHA dots (of less than 10% variation in shape diameter). The gold exposed on this MHA patterned substrate was subsequently etched (20 mM thiourea, 30 mM iron nitrate, 20 mM hydrochloric acid and 2 mM octanol) to a raised structure that was approximately 25 nm in height and easily imaged by an optical microscope. Obtained. (FIG. 2A)

A decisive feature of polymer pen lithography is that, in contrast to DPN and most contact printing strategies 21 , which are generally considered to be pressure or force independent, it exhibits ink transport that depends on both time and pressure. As in the DPN, the shape produced by polymer pen lithography shows a size that depends linearly on the square root of the tip-based contact time (FIG. 6) (27, 28) . This property of polymer pen lithography makes it possible to pattern the submicron shape with high precision and reproducibility (less than 10% change in shape size under the same experimental conditions), as a result of the diffusion properties of the ink and the small size of the transfer tip. . The pressure dependence of polymer pen lithography is derived from the compressive nature of the elastomeric pyramidal array. In fact, the tip, which is visible only under the microscope, preferably in the form of a pyramid, can deform as the amount of applied pressure is continuously increased, which can only be controlled by extending the piezoelectric (z-piezoelectric) in the vertical direction. . This deformation has been considered a major drawback of contact printing (which can result in "roof" collapse and can limit shape size resolution), but for polymer pen lithography, controlled deformation can be used as an adjustable variable, which is a tip- It is possible to control the substrate contact area and the resulting shape size. Within the pressure range allowed by the z-piezoelectric extension of about 5 to about 25 μm, a nearly linear relationship can be observed between the piezoelectric extension and shape size at a fixed contact time of 1 second (FIG. 2B). Interestingly, at the initial contact point and up to a relative extension of 0.5 μm, the MHA dot size does not change significantly, about 500 nm in all of them, which is the backside elastomer that connects all the pyramids before the pyramidal tips are deformed. Indicates that the layer is deformed. This type of cushioning is an accidental luck and essential for smoothing, as it provides additional tolerance in contacting all the tips with the surface and significantly changing the desired shape size without deformation of the tip. will be. If the z-piezo is stretched by 1 μm or more, the tip shows significant and controllable deformation. (FIG. 2B)

The pressure dependence of polymer pen lithography eliminates the need to rely on the time-consuming meniscus mediated ink diffusion process to produce large shapes. In fact, by simply adjusting the degree of deformation of the tip, it is possible to create a shape with nanometer or micrometer size in just one printing cycle. As a proof-of-concept, each square in a line is created in one print cycle at a constant tip-based contact time of 1 second at different tip-based pressures to produce a 6x6 gold square array of polymer pen lithography. And by subsequent wet chemical etching (FIG. 2C). The maximum and minimum gold squares are 4 μm and 600 nm at the corners, respectively. This experiment does not limit the range of shape sizes obtainable in polymer pen lithography experiments, but rather is a demonstration of the multiple sizes available by polymer pen lithography at a fixed tip-based contact time (in this case, 1 second). It should be noted that

Polymer pen lithography, unlike prior art contact printing, allows for the combinatorial patterning of molecular-based and solid state shapes with dynamic control over shape size, spacing, and shape. This is accomplished by using a polymer pen to form the dot pattern of the structure to be manufactured. As a proof-of-concept process, 100 integrated gold circuit replicas were created using a polymer pen array with 100 pyramidal tips spaced 1 mm apart. The width of each electrode in the center of the circuit was 500 nm, whereas the width of each electrode lead directed to this nanometer scale electrode was 10 μm and the size of the external bonding pad was 100 × 100 μm ² (FIG. 2D). Nscriptor ^TM only because it provides 90x90㎛ scanner ^2, the circuit 35 divides the lower pattern of 80x80㎛ ^2, after each of the lower pattern generated by moving manually the motor stage (stage motor) stitching them together (stitch ). This limitation can be solved by programming the movement of the stage motor with respect to the position of the plurality of lower patterns. To accommodate both resolution and throughput concerns, different relative z piezoelectric extensions were used at different locations in the circuit, with 0 (initial contact), 2, and 6 μm, respectively, for the center electrode, electrode wire, and bonding pad. It became. As a result, only 400 print jobs (less than 0.5 seconds for each job) were required to create an area of 100 × 100 μm ² , so the total time required to generate 100 circuit replicas took approximately 2 hours. The PDMS polymer acts as a reservoir for the ink throughout the experiment, so re-inking the pen array is not necessary ( 27, 28 ). This relatively high throughput production for patterns with multiple sizes is difficult if not impossible with EBL or DPN.

Due to the maskless nature of polymer pen lithography, it is possible to arbitrarily manufacture various types of structures without the difficulty of designing a new master via a throughput-impeded continuous process. In addition, polymer pen lithography can be used at resolutions below 100 nm with the registration capability of closed loop scanners. For example, 15,000 2008 Beijing Olympics logo replicas were generated on gold using polymer pen lithography, with MHA and subsequent subsequent wet chemical etching as ink (FIG. 3A). Each logo was generated using the multiscale capability of polymer pen lithography from a 70 × 60 μm ² bitmap. The letters and numbers "Beijing 2008" are generated from ~ 20,000 90nm dots (initial contact), while the figure and olympic ring parts are ~ 4000 at higher array-based contact pressures (relative piezoelectric extension = 1 μm). Made from 600 nm dots. This structure was created by holding the pen array for 0.05 seconds at each point and moving at a rate of 60 μm / sec between each point. Representative portions of approximately 15,000 replicates produced across the 1 cm 2 substrate show their uniformity (FIG. 3B). The total time needed to build all these structures was less than 40 minutes.

A new lithography method, called “polymer pen lithography”, has been developed to produce nanoscale and microscale shapes in a constructive manner using elastomeric pen arrays mounted on an inscripting device such as Nscriptor ^™ equipment. This technology combines many features of DPN and contact printing to provide patterning capabilities that include multiple length scales with high throughput and low cost. The novel time and pressure dependent ink transport properties of polymer pen pyramid arrays provide important and tunable variables that differentiate polymer pen lithography from many of the nano and micro fabrication approaches that have been developed to date. Because polymer pen lithography is a direct fabrication technique, it is also useful for the fabrication of structure arrays made of soft materials such as proteins (FIG. 7), and thus also useful in the life sciences.

Tip array

The lithographic method disclosed herein employs a tip array formed from an elastomeric polymer material. Tip arrays are non-cantilevered and can be designed to have various shapes or gaps between them as needed. The shape of each tip may be the same or different than the other tips of the array. Tip forms contemplated include spheroids, hemispheres, hemispheroids, toroids, polyhedrons, cones, cylinders and pyramids (triangles or squares). The tips are sharp so that they are suitable for forming submicron patterns of less than about 500 nm, for example. The sharpness of the tip is measured by its radius of curvature, the radius of curvature of the tips disclosed herein is less than 1 μm, less than about 0.9 μm, less than about 0.8 μm, less than about 0.7 μm, less than about 0.6 μm, less than about 0.5 μm, about Less than about 0.4 μm, less than about 0.3 μm, less than about 0.2 μm, less than about 0.1 μm, less than about 90 nm, less than about 80 nm, less than about 70 nm, less than about 60 nm, or less than about 50 nm.

The tip array can be formed from a mold made using the photolithography method, which mold is used to fabricate the tip array using the polymers disclosed herein. The mold may be made to include a large number of tips arranged in any desired manner. The tips of the tip array can be any number desired, and the number of tips contemplated can be from about 1000 tips to up to about 15 million tips or more. The number of tips in the tip array is at least about 1 million, at least about 2 million, at least about 3 million, at least about 4 million, at least about 5 million, at least about 6 million, at least about 7 million, at least about 8 million, about 9 At least one million, at least about 10 million, at least about 11 million, at least about 12 million, at least about 13 million, at least about 14 million, or at least 15 million.

The tips of the tip array may be designed to have any desired thickness, but typically the thickness of the tip array is about 50 nm to about 1 μm, about 50 nm to about 500 nm, about 50 nm to about 400 nm, about 50 nm to about 300 nm, about 50 nm to about 200 nm, or about 50 nm to about 100 nm.

The polymer may be any polymer having compressibility compatible with the lithography method. Suitable polymeric materials for use in the tip array may have a linear or branched backbone and may or may not be crosslinked, depending on the degree of compressibility required for the particular polymer and tip. Crosslinkers refer to multifunctional monomers capable of forming two or more covalent bonds between polymer molecules. Non-limiting examples of crosslinking agents include such as trimethylolpropanetrimethacrylate (TMPTMA), divinylbenzene, diepoxy, triepoxy, tetraepoxy, divinylether, trivinylether, tetravinylether and combinations thereof do.

 Thermoplastic or thermoset polymers can be used and can be crosslinked elastomers. In general, the polymer may be porous and / or amorphous. Various elastomeric polymer materials are contemplated, including polymers of the general class of silicone polymers and epoxy polymers. For example, polymers having a low glass transition temperature, such as below 25 ° C., or more preferably below −50 ° C., may be used. In addition to compounds based on aromatic amines, triazines and cyclic aliphatic backbones, diglycidyl ethers of bisphenol A can be used. Another example includes Novolac polymers. Other contemplated elastomeric polymers include methylchlorosilanes, ethylchlorosilanes and phenylchlorosilanes, polydimethylsiloxanes (PDMS). Other materials include polyethylene, polystyrene, polybutadiene, polyurethane, polyisoprene, polyacrylic rubber, fluorosilicone rubber, and fluoroelastomers.

Further examples of suitable polymers that can be used to form the tip are described in US Pat. No. 5,776,748; US Patent No. 6,596,346; And US Pat. No. 6,500,549, which are incorporated herein by reference in their entirety. Other suitable polymers are He, Langmuir 2003, 19, 6982-6986 ; Donzel et al., Adv . Mater . 2001, 13, 1164-1167; And those disclosed in Langmuir , 1998, 14-15, 3791-3795 by Martin et al. Hydrophobic polymers such as polydimethylsiloxane can be modified chemically or physically, for example by exposure to a strong oxidant solution or exposure to an oxygen plasma.

The polymers in the tip array must have an appropriate compression modulus and surface hardness to prevent the polymer from collapsing during ink application or printing, but having too high modulus and too large surface hardness will adapt to the substrate surface during printing because the material is brittle. And cannot be adapted. As disclosed in Macromolecules , 33: 3042 (2000) by Schmid et al., Vinyl and hydrosilane prepolymers can be tailored to provide polymers of different modulus and surface hardness. Thus, in some cases, the polymer is a mixture of vinyl and hydrosilane prepolymers, wherein the weight ratio of vinyl prepolymer to hydrosilane crosslinker is from about 5: 1 to about 20: 1, about 7: 1 to about 15: 1, or From about 8: 1 to about 12: 1.

Is a polymer of the tip array,: by (Schmid, such as Macromolecules, 33 3042 (2000) as described in the 3044 side) compared to the resistance of the glass surface, a surface for penetration by a steel body composition diameter 1mm (hard sphere) It is desirable to have a surface hardness of about 0.2% to about 3.5% of the glass as measured by resistance. The surface hardness may be about 0.3% to about 3.3%, about 0.4% to about 3.2%, about 0.5% to about 3.0%, or about 0.7% to about 2.7. The polymer of the tip array may have a compression modulus of about 10 MPa to about 300 MPa. Preferably the tip array may comprise a compressive polymer that is hook elastic under pressure of about 10 MPa to about 300 MPa. The linear relationship between the shape size and the pressure applied to the tip array allows for control of the indicia printed using the disclosed method and the tip array (see FIG. 2B).

The tip array may comprise a polymer having adsorption and / or absorption properties relative to the patterned composition, such that the tip array serves as its own patterned composition reservoir. PDMS, for example, is known to absorb patterned inks. (Reference: US Patent Publication No. 2004/228962, Zhang et al. Nano Lett . 4 , 1649 (2004), and Wang et al. Langmuir 19 , 8951 (2003).

The tip array can include a plurality of tips secured to a common substrate and formed from the polymers disclosed herein. The tips may be arranged randomly or in a regular periodic pattern (eg, in a matrix fashion, circular pattern, etc.). The tips may all have the same shape or may be of different shapes. The common substrate may comprise an elastomeric layer, which may include the same polymer that forms the tip of the tip array or may comprise a different elastomeric polymer than the tip array. The elastomer layer may have a thickness of about 50 μm to about 100 μm. The tip array can be attached or secured to a rigid support (eg, a glass such as a glass slide). In various cases, the common substrate, tip array, and / or rigid support, if present, are translucent or transparent. In certain cases, each of these is translucent or transparent. The combined thickness of the tip array and the common substrate is less than 200 μm, preferably less than about 150 μm, or more preferably about 100 μm.

Patterning composition

Patterning compositions suitable for use in the disclosed methods include both homogeneous and heterogeneous compositions, the latter of which refers to compositions having more than one component. The patterning composition is coated over the tip array. As used herein, the term "coating" refers to both the adsorption and absorption by the tip array of the patterned composition as well as the coating of the tip array. When coating the tip array with the patterning composition, the patterning composition can be patterned on the substrate surface using the tip array.

The patterning composition can be liquid, solid, semi-solid, and the like. Patterning compositions suitable for use include molecular solutions, polymer solutions, pastes, gels, creams, glues, resins, epoxies, adhesives, metal films, particulates, solders, etchant and combinations thereof It is not limited to this.

Patterning compositions may be monolayer-forming species, thin-film forming species, oils, colloids, metals, metal complexes, metal oxides, ceramics, organic species (e.g., small molecules, polymers, polymer precursors, proteins, antibodies, etc.). Residues comprising carbon-carbon bonds), polymers (eg, non-biological polymers and biological polymers such as single and double chain DNA, RNA, etc.), polymer precursors, dendrimers, nanoparticles, and combinations thereof Includes but is not limited to materials. In some embodiments, one or more components of the patterning composition are formed, for example, by the formation of chemical bonds, by ionic interactions, by van der Waals interactions, by electrostatic interactions, by magnetic forces, By adhesion, and by a combination thereof, to include functional groups suitable for connection with the substrate.

In some embodiments, the composition is formulated to adjust its viscosity. Parameters that can control the ink viscosity include solvent composition, solvent concentration, thickener composition, thickener concentration, particle size of the component, molecular weight of the polymer component, degree of crosslinking of the polymer component, free volume of the component (ie porosity), swelling of the component , Ionic interactions between ink components (eg, solvent-thickener interactions), and combinations thereof.

In some embodiments, the patterned composition comprises additives such as solvents, thickeners, ionic species (eg, cations, anions, zwitterions, etc.), the concentrations of which are viscosity, dielectric constant, conductivity, tonicity ), Density, etc. may be selected to adjust.

Suitable thickeners include metal salts of carboxyalkylcellulose derivatives (eg sodium carboxymethylcellulose), alkylcellulose derivatives (eg methylcellulose and ethylcellulose), partially oxidized alkylcellulose derivatives (eg hydroxy ethyl Cellulose, hydroxypropylcellulose and hydroxypropylmethylcellulose), starch, polyacrylamide gel, homopolymer of poly-N-vinylpyrrolidone, poly (alkyl ether) (e.g. polyethylene oxide, polyethylene glycol, And polypropylene oxide), agar, agarose, xanthan gum, gelatin, dendrimers, colloidal silicon dioxide, lipids (eg, fats, oils, steroids, waxes, oleic acid, linoleic acid) Glycerides, phosphocholines of fatty acids such as linolenic acid and arachidonic acid It comprises a lipid bilayer), and combinations thereof, such as from, but are not limited thereto. In some embodiments, the thickener is present at a concentration of about 0.5% to about 25%, about 1% to about 20%, or about 5% to about 15% by weight of the patterning composition.

Suitable solvents for the patterning composition include water, C1-C8 alcohols (eg methanol, ethanol, propanol and butanol), C6-C12 straight chain, branched and cyclic hydrocarbons (eg hexane and cyclohexane ), C6-C14 aryl and aralkyl hydrocarbons (eg benzene and toluene), C3-C10 alkyl ketones (eg acetone), C3-C10 esters (eg ethylacetate), C4-C10 alkyl Ethers, and combinations thereof, including but not limited to. In some embodiments, the solvent is about 1% to about 99%, about 5% to about 95%, about 10% to about 90%, about 15% to about 95%, about 25% to about by weight of the patterned composition. 95%, about 50% to about 95%, or about 75% to about 95%.

The patterning composition may comprise an etchant. As used herein, the term “etchant” refers to a component that can react with a surface to remove a portion of the surface. Thus, the etchant reacts with the surface and at least one of volatile and / or soluble materials that can be removed from the surface, or residues, or particulates, or fragments that can be removed from the substrate, for example, by rinsing or cleaning methods. It is used to form a subtractive feature by forming a. In some embodiments, the etchant is about 0.5% to about 95%, about 1% to about 90%, about 2% to about 85%, about 0.5% to about 10%, or about 1% by weight of the patterning composition. To about 10%.

Suitable etchant for use in the methods disclosed herein include, but are not limited to, acidic etchant, basic etchant, fluoride-based etchant, and combinations thereof. Acidic etching agents suitable for use with the present invention include sulfuric acid, trifluoromethanesulfonic acid, fluorosulfonic acid, trifluoroacetic acid, hydrofluoric acid, hydrochloric acid, carborane acid, and combinations thereof. However, the present invention is not limited thereto. Basic etching agents suitable for use with the present invention include, but are not limited to, sodium hydroxide, potassium hydroxide, ammonium hydroxide, tetraalkylammonium hydroxide ammonia, ethanolamine, ethylenediamine, and combinations thereof It doesn't work. Fluoride-based etchants suitable for use with the present invention include ammonium fluoride, lithium fluoride, sodium fluoride, potassium fluoride, rubidium fluoride, cesium fluoride, francium fluoride, antimony fluoride, calcium fluoride, Ammonium tetrafluoroborate, potassium tetrafluoroborate and combinations thereof.

In some embodiments, the patterned composition comprises a reactive component. As used herein, the term "reactive component" refers to a compound or species that has a chemical interaction with the substrate. In some embodiments, reactive components in the ink penetrate or diffuse into the substrate. In some embodiments, the reactive component modifies or binds to or promotes binding to functional groups exposed on the substrate surface. Reactive components can include, but are not limited to, ions, free radicals, metals, acids, bases, metal salts, organic reagents, and combinations thereof. The reactive component further includes, but is not limited to, monolayer forming species such as thiols, hydroxides, amines, silanols, siloxanes, and the like, and other monolayers known to those of ordinary skill in the art. The reactive component is about 0.001% to about 100%, about 0.001% to about 50%, about 0.001% to about 25%, about 0.001% to about 10%, about 0.001% to about 5%, about by weight of the patterned composition 0.001% to about 2%, about 0.001% to about 1%, about 0.001% to about 0.5%, about 0.001% to about 0.05%, about 0.01% to about 10%, about 0.01% to about 5%, about 0.01% To about 2%, about 0.01% to about 1%, about 10% to about 100%, about 50% to about 99%, about 70% to about 95%, about 80% to about 99%, about 0.001%, about It may be present at a concentration of 0.005%, about 0.01%, about 0.1%, about 0.5%, about 1%, about 2%, or about 5%.

The patterned composition may further comprise conductive and / or semi-conductive components. As used herein, the term "conductive component" refers to a compound or species capable of transferring or transferring charge. Conductive and semiconductive components include, but are not limited to, metals, nanoparticles, polymers, cream solders, resins, and combinations thereof. In some embodiments, the conductive component is about 1% to about 100%, about 1% to about 10%, about 5% to about 100%, about 25% to about 100%, about 50% to the weight of the patterning composition It is present at a concentration of about 100%, about 75% to about 99%, about 2%, about 5%, about 90%, about 95%.

Suitable metals for use in the patterning composition include, but are not limited to, transition metals, aluminum, silicon, phosphorus, gallium, germanium, indium, tin, antimony, lead, bismuth, alloys thereof, and combinations thereof.

In some embodiments, the patterned composition comprises a semiconductive polymer. Semiconductive polymers suitable for use with the present invention include polyaniline, poly (3,4-ethylenedioxythiophene) -poly (styrenesulfonate), polypyrrole, arylenevinylene polymers, polyphenylene vinylene, polyacetylene, Polythiophene, polyimidazole, and combinations thereof.

The patterning composition may comprise an insulating component. As used herein, the term "insulating component" refers to a compound or species that resists the transfer or transfer of charge. In some embodiments, the insulating component is about 1.5 to about 8 about 1.7 to about 5, about 1.8 to about 4, about 1.9 to about 3, about 2 to about 2.7, about 2.1 to about 2.5, about 8 to about 90, about Has a dielectric constant of 15 to about 85, about 20 to about 80, about 25 to about 75, or about 30 to about 70. Insulating components suitable for use in the methods disclosed herein include, but are not limited to, polymers, metal oxides, metal carbides, metal nitrides, monomeric precursors thereof, particles thereof, and combinations thereof. Suitable polymers include, but are not limited to, polydimethylsiloxanes, silsesquioxan, polyethylene, polypropylene, polyimide, and combinations thereof. In some embodiments, for example, the insulating component is about 1% to about 95%, about 1% to about 80%, about 1% to about 50%, about 1% to about 20%, by weight of the patterning composition, About 1% to about 10%, about 20% to about 95%, about 20% to about 90%, about 40% to about 80%, about 1%, about 5%, about 10%, about 90%, or about Present at a concentration of 95%.

The patterning composition may comprise a masking component. As used herein, the term "masking component" refers to a compound or species that forms a surface shape that resists species that may react with the surrounding surface upon reaction. Masking components suitable for use with the present invention include materials commonly employed as "resists" in traditional photolithography methods (eg, photoresists, chemical resists, self-assembled monolayers, and the like). Masking components suitable for use in the methods disclosed herein include polymers such as polyvinylpyrrolidone, poly (epichlorohydrin-co-ethyleneoxide), polystyrene, poly (styrene-co-butadiene), poly (4-vinylpyridine -co-styrene), amine-terminated poly (styrene-co-butadiene), poly (acrylonitrile-co-butadiene), styrene-butadiene-styrene block copolymer, styrene-ethylene-butylene block linear copolymer, polystyrene- Block-poly (ethylene-ran-butylene) -block-polystyrene, poly (styrene-co-maleic anhydride), polystyrene-block-poly (ethylene-ran-butylene) -block-polystyrene-graft-maleic acid Anhydrides, polystyrene-block-polyisoprene-block-polystyrene, polystyrene-block-poly (ethylene-ran-butylene) -block-polystyrene, polynorbornene, dicarboxy terminated poly (acrylonitrile-co-butadiene-co- Acrylic acid), dicarboxy-terminated poly (arc) Rylonitrile-co-butadiene), polyethyleneimine, poly (carbonate urethane), poly (acrylonitrile-co-butadiene-co-styrene), poly (vinylchloride), poly (acrylic acid), poly (methylmethacryl Rate), poly (methylmethacrylate-co-methacrylic acid), polyisoprene, poly (1,4-butylene terephthalate), polypropylene, poly (vinyl alcohol), poly (1,4-phenylenesulfide ), Polylimonene, poly (vinyl alcohol-co-ethylene), poly [N, N '-(1,3-phenylene) isophthalamide], poly (1,4-phenylene ether-ether- Sulfone), poly (ethylene oxide), poly [butylene terephthalate-co-poly (alkylene glycol) terephthalate], poly (ethylene glycol) diacrylate, poly (4-vinylpyridine), poly (DL-lac Tide), poly (3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride-co-4,4'-oxydianiline / 1,3-phenylenediamine), agarose, polyvinyl Lee Fluoride homopolymers, styrene-butadiene copolymers, phenol resins, ketone resins, 4,5-difluoro-2,2-bis (trifluoromethyl) -1,3-dioxane, salts thereof, and these Combinations of, but not limited to. In some embodiments, the masking component is present at a concentration of about 1% to about 10%, about 1% to about 5%, or about 2% by weight of the patterning composition.

The patterning composition may comprise a conductive component and a reactive component. For example, the reactive component may be one of: penetration of the conductive component into the surface, reaction between the conductive component and the surface, adhesion between the conductive shape and the surface, promotion of electrical contact between the conductive shape and the surface, and combinations thereof. The above can be improved. The surface shape formed by reacting such a patterning composition is made up of additive non-penetrating, additive penetrating, subtractive penetrating, and conformal penetrating surface shapes. It includes a conductive shape selected from the group.

For example, the patterning composition, suitable for producing a subtractive surface shape having a conductive shaped inset therein, may include an etchant and a conductive component.

The patterning composition may comprise an insulating component and a reactive component. For example, the reactive component may be one or more of penetration of the insulating component into the surface, reaction between the insulating component and the surface, adhesion between the insulating shape and the surface, promotion of electrical contact between the insulating shape and the surface, and a combination thereof. Can improve. The surface shape formed by reacting such a patterning composition includes an insulating shape selected from the group consisting of additional non-invasive, additional permeability, subtractive permeability, and conformal permeable surface shapes.

For example, the patterning composition, suitable for producing a subtractive surface shape having an insulating shape insert therein, may include an etchant and an insulating component.

For example, a patterning composition suitable for producing an electrically conductive masking shape on a surface can include a conductive component and a masking component.

Other contemplated components of the patterning composition suitable for use with the disclosed methods include thiols, 1,9-nonanedithiol solutions, silanes, silazanes, alkynes cystamines, N-Fmoc protected aminos. Thiols, biomolecules, DNA, proteins, antibodies, collagen, peptides, biotin and carbon nanotubes.

For a description of patterning compounds and patterning compositions, and their preparation and use, see Angew. Xia and Whitesides. Chem. Int. Ed., 37, 550-575 (1998) and references cited therein; Curr, Bishop et al. Opinion Colloid & Interface Sci., 1, 127-136 (1996); Calvert, J. Vac. Sci. Technol. B, 11, 2155-2163 (1993); Ulman Chem. Rev., 96: 1533 (1996) (alkanthiols on gold); Annu, Dubois et al. Rev. Phys. Chem., 43: 437 (1992) (alkanthiols on gold); An Introduction to Ultrathin Organic Films: From Langmuir-Blodgett to Self-Assembly (Academic, Boston, 1991) by Ulman (Alcanthiol on Gold); Chemical Research by Whitesides Minutes of the 39th Conference of the Robert A. Welch Foundation (Houston, Texas) Conference on Nanophase Chemistry, pp. 109-121 (1995) (alkanediol attached to gold); Mucic et al. Chem. Commun. 555-557 (1996) (describes a method of attaching 3 'thiol DNA to a gold surface); US Patent No. 5,472,881 (binding of oligonucleotide-phosphothiolate to the gold surface); Chemical Technology, Burwell, 4, 370-377 (1974) by Burwell and J. Am. By Matteucci and Caruthers. Chem. Soc., 103, 3185-3191 (1981) (binding of oligonucleotide-alkylsiloxanes to silica and glass surfaces); Grabar et al. Anal. Chem., 67, 735-743 (binding of aminoalkylsiloxanes and similar binding of mercottoalkylsiloxanes); J. Am. Chem. Soc., 109, 2358 (1987) (disulfide on gold); Langmuir of Allara and Nuzzo, 1, 45 (1985) (carboxylic acid on aluminum); J. Colloid Interfate Sci., 49, 410-421 (1974) (Carboxylic Acid on Copper) by Allara and Tompkins; The Chemistry Of Silica, Chapter 6, Iler (Wiley 1979) (carboxylic acids on silica); J. Phys. By Timmons and Zisman. Chem., 69, 984-990 (1965) (carboxylic acid on platinum); J. Am. Of Soriaga and Hubbard. Chem. 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(Thiol attachment to superconductor); United States Patent No. 5,846,909 to McDevitt et al. (Amine and thiol attachment to superconductors); Langmuir, 14, 6505-6511 (1998) by Xu et al. (Amine attachment to superconductor); Mirkin et al., Adv. Mater. (Weinheim, Ger.), 9, 167-173 (1997) (amine attachment to superconductor); Hovis et al. J. Phys. Chem. B, 102, 6873-6879 (1998) (olefin and diene attachment to silicon); Surf, Hovis et al. Sci., 402-404, 1-7 (1998) (olefin and diene attachment to silicon); Hovis et al. J. Phys. Chem. B, 101, 9581-9585 (1997) (olefin and diene attachment to silicon); J. Phys. Chem. B, 101, 1489-1492 (1997) (olefin and diene attachment to silicon); United States Patent No. 5,908,692 to Hamers et al. (Olefins and diene attachment to silicon); J. Phys. Chem. B, 103, 6243-6251 (1999) (isothiocyanate attachment to silicon); J. Phys. Chem. B, 102, 8510-8518 (1998) (adhesion of azoalkanes to silicon); Mol., Ohno. Cryst. Liq. Cryst. Sci. Technol., Sect. A, 295, 487-490 (1997) (thiol attachment to GaAs); Mater by Reuter et al. Res. Soc. Symp. Proc., 380, 119-24 (1995) (thiol attachment to GaAs); Bain's Adv. Mater. (Weinheim, Fed. Repub. Ger.), 4, 591-4 (1992) (thiol attachment to GaAs); Sheen et al. J. Am. Chem. Soc., 114, 1514-15 (1992) (thiol attachment to GaAs); Jpn. Nakagawa et al. J. Appl. Phys., Part 1, 30, 3759-62 (1991) (thiol attachment to GaAs); Lunt et al., J. Appl. Phys., 70, 7449-67 (1991) (thiol attachment to GaAs); Lunt et al. J. Vac. Sci. Technol., B, 9, 2333-6 (1991) (thiol attachment to GaAs); Langmuir ACS ASAP, Yamamoto et al., Internet Edition Ia990467r (thiol attachment to InP); Gu et al. J. Phys. Chem. B, 102, 9015-9028 (1998) (thiol attachment to InP); Adzel, Menzel et al. Mater. Weinheim, Ger., 11, 131-134 (1999) (disulfide attachment to gold); Chem. Mater., 11, 33-35 (1999) (disulfide attachment to gold); Langmuir, 14, 7378-7386 (1998) by Porter et al. (Disulfide attachment to gold); Son et al. J. Phys. Chem., 98, 8488-93 (1994) (nitrile attachment to gold and silver); Langmuir, 8, 2771-7 (1992) by Steiner et al. (Nitrile attachment to gold and copper); Solomun et al., J. Phys. Chem., 95, 10041-9 (1991) (nitrile attachment to gold); Solomun et al. Ber. Bunsen-Ges. Phys. Chem., 95, 95-8 (1991) (nitrile attachment to gold); Inorg, Henderson et al. Chim. Acta, 242, 115-24 (1996) (isonitrile attachment to gold); J. Phys. Chem. B, 103, 10489-10495 (1999) (isonitrile attachment to gold); Langmuir, 8, 357-9 (1992) by Hickman et al. (Isonitrile attachment to platinum); Langmuir, 8, 90-4 (1992) by Steiner et al. (Amine and phosphine attachments to gold and amine attachments to copper); J. Phys. Chem. B, 101, 9790-9793 (1997) (amine attachment to gold and silver); Langmuir, 15, 1075-1082 (1999) by Chen et al. (Carboxylate attachment to gold); J. Am. Of Tao. Chem. Soc., 115, 4350-4358 (1993) (carboxylate attachment to copper and silver); Laibinis et al. J. Am. Chem. Soc., 114, 1990-5 (1992) (thiol attachment to silver and copper); Langmuir, 7, 3167-73 (1991) by Laibinis et al. (Thiol attachment to silver); Fenter et al., Langmuir, 7, 2013-16 (1991) (thiol attachment to silver); Chang et al. Chem. Soc., 116, 6792-805 (1994) (thiol attachment to silver); Li et al. J. Phys. Chem., 98, 11751-5 (1994) (thiol attachment to silver); Report by Li et al., 24 pp (1994) (thiol attachment to silver); US Pat. No. 5,942,397 to Tarlov et al. (Thiol attachment to silver and copper); PCT Application WO / 99/48682 to Waldeck et al. (Thiol attachment to silver and copper); Langmuir, 7, 955-63 (1991) by Gui et al. (Thiol attachment to silver); Walczak et al. J. Am. Chem. Soc., 113, 2370-8 (1991) (thiol attachment to silver); Sangorgi et al. Gazz. Chim. Ital., 111, 99-102 (1981) (amine attachment to copper); Magallon et al., 215th ACS National Conference (Dallas, March 29-April 2, 1998) Abstract, COLL-048 (Amine Attachment to Copper); Langmuir, 14, 2707-2711 (1998) by Patil et al. (Amine attachment to silver); J. Phys. Chem. B, 101, 4954-4958 (1997) (amine attachment to silver); J. Phys. Chem. B. 102, 4058-4060 (1998) (alkyllithium attachment to silicon); J. Phys. Chem. B, 102, 1067-1070 (1998) (alkyllithium attachment to silicon); Chidsey's 214th ACS National Conference (Las Vegas, Nevada, September 7-September 1997) Abstract, I & EC-027 (Alkyllithium Attachment to Silicon); Song, JH, San Diego, California (1998) (Alkyllithium Attachment to Silicon Dioxide); Meyer et al. J. Am. Chem. Soc., 110, 4914-18 (1988) (amine attachment to semiconductors); Brazdil et al. J. Phys. Chem., 85, 1005-14 (1981) (amine attachment to semiconductors); Langmuir, 14, 741-744 (1998) by James et al. (Protein and peptide attachment to glass); Langmuir, 14, 2225-2229 (1998) by Bernard et al. (Protein adhesion to glass, polystyrene, gold, silver and silicon wafers); J. Mater, Pereira et al. Chem., 10, 259 (2000) (silazane attachment to SiO ₂ ); J. Mater, Pereira et al. Chem., 10, 259 (2000) (silazane attachment to SiO ₂ ); Dammel's Diazonaphthoquinone Based Resists (First Edition, SPIE Optical Engineering Press, Bellingham, Washington, 1993) (silazane attachment to SiO ₂ ); Anwander et al. J. Phys. Chem. B, 104, 3532 (2000) (silazane attachment to SiO ₂ ); Slavov et al. J. Phys. See Chem., 104, 983 (2000) (silazane attachment to SiO ₂ ).

Patterning Target

Suitable substrates for use in the methods disclosed herein include metals, alloys, composites, crystalline materials, amorphous materials, conductors, semiconductors, optics, fibers, inorganic materials, glass, ceramics (eg, metal oxides, Metal nitrides, metal silicides, and combinations thereof), zeolites, polymers, plastics, organic materials, minerals, biomaterials, living tissues, bones, films thereof, thin films thereof, laminates thereof, flakes thereof folls, complexes thereof, combinations thereof, but is not limited thereto. The substrate is crystalline silicon, polycrystalline silicon, amorphous silicon, p-doped silicon, n-doped silicon, silicon oxide, silicon germanium, germanium, gallium arsenide, gallium arsenide phosphide, indium tin oxide, And a semiconductor, such as but not limited to a combination thereof. Substrates include, but are not limited to, undoped silica glass (SiO ₂ ), fluorinated silica glass, borosilicate glass, borophosphorosilicate glass, organosilicate glass, porous organosilicate glass, and combinations thereof. May contain glass. The substrate can be a non-planar substrate, such as pyrolytic carbon, reinforced carbon-carbon composites, carbon-phenolic resins, and the like, and combinations thereof. Substrates include silicon carbide, hydrogenated silicon carbide, silicon nitride, silicon carbonitride, silicon oxynitride, silicon oxycarbide, high-temperature reusable surface insulation, fibrous Refractory composite insulator tiles, toughened unipiece fibrous insulation, low temperature reusable insulation, advanced reusable surface insulation, and combinations thereof, and ceramics such as, but not limited to. . The substrate may include flexible materials such as, but not limited to, plastics, metals, composites thereof, laminates thereof, thin films thereof, flakes thereof, and combinations thereof.

Smoothing of the tip array and deposition of the patterned composition on the substrate surface

The disclosed methods are in situ imaging, similar to lithography methods (eg, dip pen lithography) based on scanning probe microscopy. situ imaging) as well as the ability, provides the ability to pattern a shape in a similar way to rapid micro-contact printing. Shapes that can be patterned range in size from sub-100 nm to 1 mm or more and can be controlled by changing the contact time and / or contact pressure of the tip array. Similar to DPN, the amount of patterned composition (measured by shape size) deposited on the substrate surface is proportional to the contact time, specifically the square root correlation with the contact time. (See FIG. 6) Unlike DPN, the contact pressure of the tip array can be used to alter the amount of patterning composition that can be deposited on the substrate surface. The contact pressure can be controlled by the z-piezoelectric of the piezoelectric scanner. (See FIG. 2B) The more pressure (or force) is applied to the tip array, the larger the shape size. Thus, any combination of contact time and contact force / pressure may provide a means for the formation of shape sizes from about 30 nm to about 1 mm or more. The ability to “manually create” or in-situ manners of such a wide range of shapes in milliseconds may be useful in the disclosed lithography methods for electronic devices (eg, circuit patterning) and biotechnology (eg, biological assays). Array of targets) to make it adaptable to a host of lithographic applications. The contact pressure of the tip array can be about 10 MPa to about 300 MPa.

At very low pressures, such as from about 0.01 to about 0.1 g / cm 2 for the preferred materials disclosed herein, the shape size of the final indicia is independent of the contact pressure, so that the tip array is placed on the substrate surface without changing the shape size of the indicia. Can be smoothed. This low pressure can be achieved by an extension of 0.5 μm or less of the z-piezoelectric of the piezoelectric scanner on which the tip array is mounted, and a pressure of 0.01 g / cm 2 to about 0.1 g / cm 2 is required for z-piezoelectric extension of less than 0.5 μm. Can be applied by Due to this "buffer" pressure range, the tip array, substrate, or both are adjusted to achieve initial contact between the tip and the substrate surface without compressing the tip, and then (observed by a change in the reflection of light from the inner surface of the tip). The degree of compression of the tip can be used to achieve a uniform degree of contact between the tip and the substrate surface. This smoothing ability is important because uneven contact of the tips of the tip array can result in uneven indicia. Given the large number of tip arrays (eg, 11 million in the embodiments provided herein) and their small size, it may be difficult or impossible in practical matters to clearly know whether all the tips are in contact with the surface. For example, defects in the tip or substrate surface or irregularities in the substrate surface may result in one tip not coming in contact while all other tips are in uniform contact. Thus, the disclosed method allows at least substantially all of the tips to contact (eg, to a detectable degree) the substrate surface. For example, at least 90%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99% of the tips will be in contact with the substrate surface.

Smoothing the tip array and the substrate surface relative to each other is accomplished from the top of the tip array (ie, at the base of the tip and on the back of the common substrate) to the substrate surface using a transparent or at least translucent tip array and an array of common substrates. This can be aided by the fact that changes in the reflection of the light induced can be observed. The intensity of the light reflected from the tips of the tip array is greater upon contact with the substrate surface. (Eg, the inner surface of the tip array reflects light differently upon contact). Perform all or substantially all of the tip contact of the tip array with respect to the substrate surface by observing a change in the reflection of the light at the individual tip. The tip array and / or substrate surface can be adjusted to achieve this. Thus, the tip array and common substrate are preferably translucent or transparent, allowing to detect changes in the light reflection of the tip upon contact with the substrate surface. Likewise, all rigid backing materials on which the tip array is mounted are also preferably at least transparent or translucent.

The contact time for the tip may be about 0.001 seconds to 60 seconds depending on the amount of patterning composition required at any particular point on the substrate surface. The contact force can be controlled by varying the z-piezoelectric of the piezoelectric scanner or by other means that allow for controlled application of the force across the tip array.

The substrate surface may be in contact with the tip array multiple times, with the tip array, the substrate surface, or both, moving so that different portions of the substrate surface may contact. The time and pressure of each contacting step can be the same or different depending on the desired pattern. The shape of the indicia or pattern has no practical limit and may include dots, lines (eg, straight or curved lines formed from individual points or continuous lines), preselected patterns, or a combination thereof.

The indicia obtained from the disclosed method has a high degree of identity and is therefore uniform or substantially uniform in size and preferably in form. The shape size (eg dot width or line width) of the individual indicia is very uniform such that the tolerance is within about 5%, or about 1% or about 0.5%, for example. Tolerance may be about 0.9%, about 0.8%, about 0.7%, about 0.6%, about 0.4%, about 0.3%, about 0.2%, or about 0.1%. Non-uniformity of shape size and / or shape may result in roughness of indicia that may be undesirable for submicron type patterning.

Shape sizes range from about 10 nm to about 1 mm, about 10 nm to about 500 μm, about 10 nm to about 100 μm, about 50 nm to about 100 μm, about 50 nm to about 50 μm, about 50 nm to about 10 μm, about 50 nm to about 5 μm Or from about 50 nm to about 1 μm. The shape size may be less than 1 μm, less than about 900 nm, less than about 800 nm, less than about 700 nm, less than about 600 nm, less than about 500 nm, less than about 400 nm, less than about 300 nm, less than about 200 nm, less than about 100 nm, or less than about 90 nm.

Example

Polymer  Fabrication of the Pen Array Master:

Shipley 1805 (MicroChem, Inc.) photoresist was spin coated onto a gold thin film substrate (10 nm Cr adhesive layer with 100 nm Au thermally evaporated on a pre-purified Si <100> wafer). Square well arrays were made by photolithography using a chrome mask. The photoresist pattern was developed in MF319 developer (MicroChem, Inc.) and then exposed to O ₂ plasma for 30 seconds (200 m Torr) to remove residual organic layer. Subsequently, the substrates were placed in gold (Type TFA, Transene) and chromium (Type 1020, Transene) etching solutions, respectively. After each etching step a large amount of rinse was required with MiliQ water to purify the surface. The photoresist was then washed away with acetone to expose the gold pattern. The gold pattern substrate was placed in KOH etching solution (30% KOH in H ₂ O: IPA (4: 1 v / v)) at ˜25 min at 75 ° C. and vigorously stirred. The uncovered regions of the Si wafers were anisotropically etched to form recessed pyramids. Residual Au and Cr layers were removed by wet chemical etching. Finally the pyramid master was modified to 1H, 1H, 2H, 2H-perfluorodecyltrichlorosilane (Gelest, Inc.) by gas phase silanization.

Polymer  Fabrication of Pen Arrays :

Hard PDMS ( h- PDMS) (1,2) was used for polymer pen array fabrication. h- PDMS consisted of 3.4 g of vinyl-compound-rich prepolymer (VDT-731, Gelest) and 1.0 g of hydrosilane-rich crosslinker (HMS-301). The preparation of polymers generally involves a 20 ppm w / w platinum catalyst for the vinyl fraction (platinumdivinyltetramethyldisiloxane complex in SIP, SIP6831.1 Gelest) and a 0.1% w / w modulator for the mixture (2 , 4,6,8-tetramethyltetravinylcyclotetrasiloxane, Fluka). The mixture was stirred, degassed and poured on top of the polymer pen array master. Subsequently, a pre-purified glass slide (VWR, Inc.) was placed on top of the elastomer array and the entire assembly was cured overnight at 70 ° C. The polymer pen array was carefully separated from the pyramid master and used for lithography experiments. The procedure for manufacturing the pen array is shown in FIG. 1A.

Polymer  Protein Array Patterning by Pen Array :

Tetramethylrhodamine 5- (and-6) -isothiocyanate (TRITC) conjugated anti mouse IgG arrays were generated on a Codelink ™ glass slide (GE Healthcare) by polymer pen lithography. In a general experiment, polymer pen arrays were modified with polyethylene glycol silanes (PEG-silanes) to minimize non-specific interactions between proteins and PDMS surfaces. To perform the surface modification, the polymer pen array was briefly exposed to oxygen plasma (30 seconds) to make the surface hydrophilic. It was then immersed in 1 mM PEG-silane aqueous solution (pH 2, MW 2,000, Rapp Polymere, Germany) for 2 hours, washed with deionized water and then blown with N ₂ to dry. An aqueous solution consisting of 50 mg / ml glycerol and 5 mg / ml TRITC conjugated IgG was then spin coated onto a PEG-silane modified polymer pen array (1,000 rpm, 2 minutes) and the protein array was placed on a Codelink ™ slide using a pen array. Generated. The pen array was smoothed by monitoring the tip array through a glass slide support. When the tip is in contact with the substrate surface, the amount of light reflected from the tip is significantly increased, making it easy to monitor when all or a significant number of tips are in contact with the substrate surface (eg, when the tip is "smoothed"). Could. The patterned environment maintained a relative humidity of 70% at 20 ° C. After the polymer pen lithography process, Codelink ™ slides were incubated overnight in a humidity chamber and rinsed with 0.02% sodium dodecyl sulfate to remove the physisorbed material. 7 shows a fluorescence image of the generated 3 × 3 IgG array. Each IgG dot was prepared by contacting the tip array with the substrate for 3 seconds. The size of each IgG dot was 4 ± 0.7 micrometers.

The foregoing has described and illustrated the invention, but is not intended to limit the invention as defined by the following claims. All methods disclosed and claimed may be practiced and performed without undue experimentation in light of the present disclosure. Although the materials and methods of the present invention have been described in terms of particular embodiments, it is to be understood that the steps and order of steps of the materials and / or methods and methods described herein may be altered without departing from the spirit, scope and scope of the invention. It will be apparent to those of ordinary skill in the art. More specifically, certain chemically and physiologically related agents may be substituted for the formulations described herein and will achieve the same or similar results.

All patents, publications, and references cited herein are hereby fully incorporated by reference. In case of conflict between the patent, publication, and reference incorporated herein, the present disclosure is governed.

Claims (45)

Coating a tip array comprising a compressible elastomeric polymer comprising a plurality of non-cantilevered tips, each having a radius of curvature of less than about 1 μm with a patterning composition;
All or substantially all of the coated tips deposit the patterned composition on the substrate surface and form a substantially uniform, indicia with a dot size (or line width) of less than 1 μm. Contacting all or substantially all of the coated tips of the array during a first contact period and at a first contact pressure. The method of claim 1,
And the tip array comprises a plurality of tips arranged in a regular periodic pattern. The method according to claim 1 or 2,
Wherein each tip has a radius of curvature of less than about 0.2 μm. 4. The method according to any one of claims 1 to 3,
Wherein the polymer has a compression modulus of about 10 MPa to about 300 MPa. The method according to any one of claims 1 to 4,
And wherein said polymer is crosslinked. The method according to any one of claims 1 to 4,
Wherein said polymer comprises polydimethylsiloxane (PDMS). The method of claim 6,
Wherein said PDMS comprises a trimethylsiloxy terminated vinylmethylsiloxane-dimethylsiloxane copolymer, methylhydrosiloxane-dimethylsiloxane copolymer or mixtures thereof. The method according to any one of claims 1 to 7,
Wherein each tip of the tip array is of the same shape. The method of claim 8,
The tip shape is characterized in that the pyramid. The method according to any one of claims 1 to 9,
And wherein said coating step includes adsorbing or absorbing said patterned composition onto said tip array. The method according to any one of claims 1 to 10,
Moving the tip array, the substrate surface, or both, and repeating the contacting step during a second contacting period and at a second contacting pressure. The method of claim 11,
The first contact period and the second contact period are the same. The method of claim 11,
And wherein the first contact period and the second contact period are different. The method according to any one of claims 11 to 13,
The first contact pressure and the second contact pressure are the same. The method according to any one of claims 11 to 13,
And wherein the first contact pressure and the second contact pressure are different. The method according to any one of claims 1 to 15,
Controlling the z-piezoelectric of the piezoelectric scanner on which the substrate or the tip array is mounted to control the contact pressure. The method according to any one of claims 11 to 16,
Moving the tip array and keeping the substrate surface at rest. The method according to any one of claims 11 to 16,
Maintaining the tip array at rest and moving the substrate surface. The method according to any one of claims 11 to 16,
Moving both the tip array and the substrate surface. The method according to any one of claims 1 to 19,
Limiting lateral movement between the tip array and the substrate to form an indicia comprising dots. The method of claim 20,
Controlling the contact period, the contact pressure, or both to form the dot having a diameter in the range of about 10 nm to about 500 μm. The method according to any one of claims 1 to 19,
Controlling lateral movement between the tip array and the substrate surface during the contacting step and / or between one or more sets of contacting and depositing steps to form indicia comprising one or more lines and a preselected pattern. How to feature. The method according to any one of claims 1 to 22,
Selecting for the tip array, a compressive polymer that is hook elastic under pressure of 10 MPa to 300 MPa. The method according to any one of claims 1 to 23,
Contacting each tip of the tip array with the substrate surface. The method according to any one of claims 1 to 24,
The indicia has a dot size (or line width) of less than 900 nm. The method according to any one of claims 1 to 25,
The indicia has a dot size (or line width) of less than 100 nm. The method according to any one of claims 1 to 26,
Backlighting the tip array with incident light to cause internal reflection of incident light from the inner surface of the tip;
Bringing the tip and the substrate surface of the tip array together along a z-axis to a point of contact between the subset of the tips and the substrate surface, wherein the contact is the subset of the tips that are in contact with the substrate surface. As indicated by the increased intensity of the light reflected from it while no change in the intensity of the reflected light from the other tip indicates a non-contact tip);
To achieve contact between the non-contact tip and the substrate surface, one or both of the tip array and the substrate surface are tilted relative to each other in response to a difference in intensity of the reflected light from the inner surface of the tip. And the tilting is performed at least once along the x, y and / or z axis to smooth the tips of the tip array with respect to the substrate surface. The method according to any one of claims 1 to 26,
Back illuminating the tip array with incident light to cause internal reflection of incident light from the inner surface of the tip;
Bringing the tip of the tip array and the substrate surface together along a z axis to effect contact between the tip of the tip array and the substrate surface;
One or both of the tip array and the substrate are further moved along the z-axis toward each other to compress the subset of tips such that the intensity of reflected light from the tips is dependent upon the compression of the tip relative to the substrate surface. Increases as a function of degree;
Tilt one or both of the tip array and the substrate surface with respect to each other in response to a difference in intensity of the reflected light from the inner surface of the tip to achieve a substantially uniform contact between the substrate surface and the tip. Wherein the tilting further comprises smoothing the tip of the tip array with respect to the substrate surface by performing one or more times along the x, y, and / or z axis. A plurality of tips secured to a common substrate layer, wherein the tip and the common substrate layer are formed from an elastomeric polymer, wherein the elastomeric polymer of the tip has a compression modulus of about 10 MPa to about 300 MPa, each tip having about 1 Tip array, characterized in that it has a radius of curvature of less than μm. The method of claim 29,
Each tip has a radius of curvature of less than about 0.5 μm. The method of claim 30,
Each tip has a radius of curvature of less than about 100 nm. The method of any one of claims 29 to 31,
And the tips are arranged in a regular periodic pattern. 33. The method according to any one of claims 29 to 32,
Tip array, characterized in that the tip is the same shape. The method according to any one of claims 29 to 33, wherein
And the tip is pyramidal in shape. 36. The method of any of claims 29 to 35,
And the thickness of the common substrate layer is about 50 μm to about 100 μm. 36. The method of any of claims 29 to 35,
And a rigid support to which the common substrate is fixed. The method according to any one of claims 29 to 36,
And the tip array, common substrate layer and rigid support are at least translucent. The method according to any one of claims 29 to 37,
And the common substrate layer and the tip have a combined thickness of less than about 200 μm. The method of claim 38,
And the combined thickness is less than about 150 μm. The method of claim 39,
And the combined thickness is about 100 μm. A plurality of tips fixed to a common substrate layer, wherein the tips and the common substrate layer are formed from an elastomeric polymer, each tip having a radius of curvature of less than about 1 μm, and the common substrate layer and the tip about 200 μm Tip array having a combined thickness of less than. And a translucent laminated structure comprising a plurality of tips secured to a common elastomeric polymer substrate, wherein the substrate is secured to a glass slide. Forming a master comprising an array of recesses in the substrate spaced by lands;
Filling said recess with a prepolymer mixture comprising a prepolymer and optionally a crosslinking agent and covering said lands;
Curing the prepolymer mixture to form a polymer structure; And
Separating the polymer structure from the master. The method of claim 44,
Forming wells in said substrate and forming said recesses into pyramidal recesses by anisotropically wet etching said substrate. 46. The method of claim 44 or 45,
And covering said filled and coated substrate with a planar glass layer prior to curing.

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